Landfill disposal of municipal solid waste incineration fly ash (MIFA) presents significant environmental and economic burden. This study proposed a novel and high-efficiency approach for stabilisation/solidification (S/S) of MIFA by phosphate-modified calcium aluminate cement (CAC). Experimental results showed that the presence of Pb (the most leachable metal contaminant in the MIFA) retarded the early-stage reaction of CAC, resulting in an extension of setting time and a significant decline of compressive strength of CAC pastes. The incorporation of phosphate additives (10 wt% of binder), especially for trisodium phosphate, in CAC system effectively mitigated the negative impact of Pb on the CAC reaction and reduced the Pb leachability. Elemental mapping results illustrated that Pb²⁺ coordinated with phosphate to generate insoluble precipitates (e.g., Pb₃(PO₄)₂). The S/S treated MIFA samples fulfilled the compressive strength and leachability requirements for on-site reuse. Overall, this study demonstrated that phosphate-modified CAC is a promising binder for S/S of hazardous MIFA.